FR2929266A1 - MESOSTRUCTURE MATERIAL WITH A HIGH ALUMINUM CONTENT AND CONSISTING OF SPHERICAL PARTICLES OF A SPECIFIC SIZE - Google Patents

Abstract

A mesostructured material consisting of at least two elementary spherical particles is described, each of said particles comprising a mesostructured matrix based on aluminum oxide, said matrix having a pore diameter of between 1.5 and 30 nm and a content of aluminum oxide representing more than 46% by weight relative to the mass of said matrix, which has amorphous walls with a thickness of between 1 and 30 nm, said elementary spherical particles having a diameter D greater than 10 μm and less than or equal to at 100 & mum (10 <D (& mum) <= 100). Said mesostructured matrix may also contain silicon oxide. Each of the spherical particles of the mesostructured material may also contain zeolite nanocrystals so as to form a mixed porosity material of both mesostructured and zeolitic nature. The preparation of said material is also described.

Description

TECHNICAL FIELD The present invention relates to the field of mesostructured materials based on aluminum oxide. It also relates to the field of mesostructured materials with a high aluminum content having a hierarchical or mixed porosity in the field of microporosity and mesoporosity. It also relates to the preparation of these materials which are obtained by the use of the "EISA" method (Evaporation Induced by Self Assembly) also called self-assembly method induced by evaporation. The structural and textural properties of the materials according to the invention as well as their acid-base properties make them particularly suitable for applications in the field of refining and petrochemistry. STATE OF THE PRIOR ART The new synthesis strategies making it possible to obtain materials with well-defined porosity in a very wide range, ranging from microporous materials to macroporous materials, via materials with a hierarchical or mixed porosity, that is to say to say having pores of various sizes, have been very widely developed in the scientific community since the mid-1990s (GJ AA Soler-Illia, C. Sanchez, B. Lebeau, J. Patarin, Chem Rev., 2002, 102, 4093). Materials are obtained whose pore size is controlled. In particular, the development of so-called "soft chemistry" synthesis methods has led to the development of mesostructured materials at low temperature by the coexistence in aqueous solution or in polar solvents of inorganic precursors with structuring agents, generally molecular surfactants. or supramolecular, ionic or neutral. The control of electrostatic or hydrogen bonding interactions between the inorganic precursors and the structuring agent together with hydrolysis / condensation reactions of the inorganic precursor leads to a cooperative assembly of the organic and inorganic phases generating micellar aggregates of uniformly sized surfactants. and controlled within an inorganic matrix. This phenomenon of cooperative self-assembly governed, inter alia, by the concentration of structuring agent can be induced by progressive evaporation of a solution of reagents whose concentration of structuring agent is most often lower than the critical micelle concentration, which leads either to the formation of mesostructured films in the case of a deposit on substrate ("dip-coating" technique), or to the formation of a mesostructured powder after atomization (aerosol technique) or draining of the solution. By way of example, US Pat. No. 6,387,453 discloses the formation of mesostructured organic-inorganic hybrid films by the "dip-coating" technique, these same authors having also used the aerosol technique to develop mesostructured purely silicic materials ( CJ Brinker, Y. Lu, A. Sellinger, H. Fan, Adv Mater., 1999, 11, 7). The release of the porosity is then obtained by removing the surfactant, which is conventionally carried out by chemical extraction processes or by heat treatment. Depending on the nature of the inorganic precursors and the structuring agent used as well as the operating conditions imposed, several families of mesostructured materials have been developed. For example, the M41 S family originally developed by Mobil (JS Beck, JC Vartuli, WJ Roth, ME Leonowicz, CT Kresge, KD Schmitt, CT-W Chu, DH Oison, EW Sheppard, SB MC: Cullen, JB Higgins, J.

L. Schlenker, J. Am. Chem. Soc., 1992, 114, 27, 10834), consisting of mesoporous materials obtained via the use of ionic surfactants such as quaternary ammonium salts, having a generally hexagonal, cubic or lamellar structure, pores of uniform diameter included in a range from 1.5 to 10 nm and amorphous walls of thickness of the order of 1 to 2 nm has been extensively studied. Subsequently, in order to increase the hydrothermal stability properties while developing acid-base properties relating to these materials, the incorporation of the aluminum element into the amorphous silicic framework by direct synthesis or by post methods. The synthesis was particularly considered, the resulting aluminosilicate materials having a Si / Al molar ratio in the range of 1 to 1000 (S. Kawi, Shen SC, Surf Stud, Sci.

Catal., 2000, 129, 227; S. Kawi, S.C. Shen, Stud. Surf. Sci. Catal., 2000, 129, 219; R. Mokaya, W. Jones, Chem. Commun., 1997, 2185). The hydrothermal stability properties and the acid-base properties thus developed by these aluminosilicates, however, did not allow their use at an industrial stage in refining or petrochemical processes, which gradually led to the use of new structuring agents such as block copolymer type amphiphilic macromolecules, the latter leading to mesostructured materials having a generally hexagonal, cubic or lamellar structure, pores of uniform diameter in a range of 4 to 50 nm and amorphous walls of thickness in a range of 3 to 7 nm. Depending on the desired structure and degree of organization for the final mesostructured material, the synthetic methods employed may take place in an acid medium (pH 1) (WO 99/37705) or in a neutral medium (WO 96/39357), the nature of the structuring agent used also plays a leading role. The mesostructured aluminosilicate materials thus obtained have increased hydrothermal stability properties compared to their counterparts synthesized by other structuring agents, their acid-base properties remaining approximately similar (1 <Si / Al <1000). However, low values of the Si / Al molar ratio such as Si / Al <20 are difficult to obtain because it is not easy to incorporate large amounts of aluminum into the material via these particular processes (Zhao, D. J. Feng, Q. Huo, N. Melosh, GH Fredrickson, BF Chmelka, GD Stucky, Science, 1998, 279, 548, Y.-H. Yue, A. Gideon, J. -L.

Bonardet, J. B. d'Espinose, N. Melosh, J. Fraissard, Stud. Surf. Sci. Catal., 2000, 129, 209).

Much work has also been undertaken to develop aluminosilicate materials with both the advantages of an organized mesoporous structure and those of a microcrystalline network. Several synthetic techniques for the preparation of mixed materials or mesostructured composites / zeolites have thus been listed in the open literature. A first synthesis technique consists of synthesizing in the first step a mesostructured aluminosilicate material according to the conventional methods explained above and then, in the second step, impregnating this material with a structuring agent usually used in the synthesis of zeolite materials. A suitable hydrothermal treatment leads to a zeolitization of the amorphous walls (or walls) of the mesostructured aluminosilicate starting (US 6,669,924). A second synthetic technique consists in placing a colloidal solution of zeolite seeds with a structuring agent usually used to create a mesostructuration of the final material. The development of an inorganic matrix with organized mesoporosity and the growth within this matrix of zeolite seeds, so as to obtain a mesostructured aluminosilicate material having crystallized walls (or walls), are simultaneous (Z. Zhang, Y. Han, F. Xiao, S. Qiu, L. Zhu, R. Wang, Y. Yu, Z. Zhang, B. Zou, Y. Wang, Sun H., Zhao D., Y. Wei, J. Am. Chem Soc., 2001, 123, 5014; Y. Liu, W. Zhang, TJ Pinnavaia, J. Am. Chem., Soc., 2000, 122, 8791). An alternative to these two techniques initially consists in the preparation of a mixture of aluminum and silicon precursors in the presence of two structuring agents, one capable of generating a zeolite system, the other capable of generating a mesostructuring. This solution is then subjected to two crystallization steps using variable hydrothermal treatment conditions, a first step which leads to the formation of the mesoporous structure with organized porosity and a second step which leads to the zeolitization of the walls (or walls amorphs (A. Karisson, M. Stdcker, R. Schmidt, Micropor, Mesopor, Mater., 1999, 27, 181). All of these synthesis methods have the disadvantage of damaging the mesoporous structure and thus losing the advantages thereof in the case where the growth of zeolite seeds or the zeolitization of the walls is not perfectly controlled, which makes these delicate techniques to implement. It is possible to avoid this phenomenon by directly developing: mesostructured composite materials / zeolites. This can be done by heat treatment of a mixture of zeolite seed solution and mesostructured aluminosilicate seed solution (P. Prokesova, S. Mintova, J. Cejka, T. Bein, Micropor.

Mesopor. Mater., 2003, 64, 165) or by growth of a zeolite layer on the surface of a pre-synthesized mesostructured aluminosilicate (DT On, S. Kaliaguine, Angew Chem Int, Ed., 2002, 41 , 1036). From an experimental point of view, in contrast to the techniques involving the "EISA" process described above, the aluminosilicate materials with a hierarchical porosity thus defined are not obtained by a progressive concentration of the inorganic precursors and (s) structuring agent (s) within the solution where they are present but are conventionally obtained by direct precipitation in an aqueous solution or in polar solvents by varying the value of the critical micelle concentration of the structuring agent. In addition, the synthesis of these materials obtained by precipitation requires an autoclave ripening step and all the reagents are not integrated into the stoichiometric quantity products since they can be found in the supernatant. The elementary particles usually obtained do not have a regular shape and are generally characterized by a size generally ranging between 200 and 500 nm and sometimes more.

The invention relates to a mesostructured material consisting of at least two elementary spherical particles, each of said spherical particles comprising a mesostructured matrix based on aluminum oxide, said matrix having a pore diameter of between 1.5 and 30 μm. nrn and an aluminum oxide content representing more than 46% by weight relative to the mass of said matrix, which has amorphous walls with a thickness of between 1 and 30 nm, said elementary spherical particles having a diameter D such that 10 <D (μm) <100. Said mesostructured matrix based on aluminum oxide preferably comprises silicon oxide in a proportion such that the Si / Al molar ratio of said matrix is strictly less than 1.

Each of said elementary spherical particles may also comprise zeolitic nanocrystals having a pore opening of between 0.2 and 2 nm so that said material according to the invention has a mixed porosity of both mesostructured and zeolitic nature.

The present invention also relates to the preparation of the material according to the invention. The process for preparing the material according to the invention, called the "main preparation process according to the invention", comprises a) mixing in solution at least one surfactant, at least one aluminum precursor and optionally at least one precursor. silicic; b) the aerosol atomization of the solution obtained in step a) using a spray nozzle which leads to the formation of liquid droplets having a diameter less than or equal to 300 μm; c) drying said droplets, d) grinding the solid product obtained in step c); e) mixing in solution at least one surfactant, at least one aluminic precursor, optionally at least one silicic precursor and at least one fraction of the solid product obtained in step d) so as to form a suspension ; f) the aerosol atomization of the suspension obtained in step e) using a spray nozzle leading to the formation of suspension droplets, which are precursors of the spherical elementary particles having a diameter D such that 10 <D (pm 100 constituents of the material according to the invention; g) drying said droplets obtained in step f) and h) removing said surfactant introduced in said steps a) and e) to obtain a material with mesostructured porosity. Said process is hereinafter referred to as the "main process of preparation according to the invention". For the preparation of a mixed mesostructured / zeolitic material, a preliminary step ao) consisting in the synthesis, in the presence of at least one structuring agent, of zeolite nanocrystals of maximum nanometric size equal to 1000 nm is carried out in order to obtain to obtain a colloidal solution in which said nanocrystals are dispersed or zeolite crystals, which have the characteristic of dispersing in the form of nanocrystals of maximum nanometric size, can be introduced into the mixture according to steps a) and e) described above; equal to 1000 nm in solution. The ordered structure of the matrix of each of the spherical particles constituting the material according to the invention is consecutive to the phenomenon of micellization or self-assembly induced by the "EISA" method.

Interest The mesostructured material according to the invention is a material consisting of elementary spherical particles, each of said particles comprising a mesostructured matrix having a high content of aluminum. Said mesostructured matrix may also contain silicon oxide, which, in this case, gives the material according to the invention interesting acid-base properties. The present invention also provides a mixed porosity material in which zeolitic nanocrystals are trapped in the mesostructured matrix, such a material being advantageous because it simultaneously exhibits the structural, textural and acid-base properties specific to the materials of the zeolite family. and aluminum oxide materials, more particularly mesostructured aluminosilicate materials. The ordered structure of the material according to the invention being consecutive to the phenomenon of micellization or self-assembly induced by the "EISA" process, makes it possible to easily develop mesostructured materials, in the presence or absence of zeolitic nanocrystals, without damaging the nature of the mesostructured phase or that of the zeolite phase possibly present and to work with a wide range of zeolite nanocrystals regardless of their initial synthesis processes. Indeed, for the preparation of a mesostructured / zeolitic mixed porosity material, it is possible to use zeolite crystals with a size much greater than 1000 nm since they have the property of dispersing in solution, in particular in acid solution and very preferentially in aqueous-organic acid solution, in the form of nanocrystals of maximum nanometric size equal to 1000 nm. In addition, the development on a "submicron" scale of a mesostructured / zeoilithic material leads to a privileged connection of the microporous and mesoporous zones within the same spherical particle. In addition, the mesostructured material according to the invention, in the presence or absence of zeolitic nanocrystals, consists of spherical elementary particles. Said particles have a diameter D such that 10 <D (μm) <100 and preferably D is between 11 and 70 μm. The controllable size of these particles resulting from the implementation and control of the "EISA" process by the applicant, as well as their perfectly spherical shape, allow for better control of the diffusion of the compounds when the material is used. according to the invention as catalyst or adsorbent for applications in the field of refining and petrochemistry, compared to materials known in the state of the art being in the form of elementary particles of inhomogeneous form, that is, to say irregular. In addition, compared to the known syntheses of the mesostructured materials, the preparation of the material according to the invention is carried out continuously, the preparation time is reduced (a few hours compared with 12 to 24 hours using autoclaving) and the stoichiometry of the Non-volatile species present in the initial solution of the reagents is maintained in the material of the invention. SUMMARY OF THE INVENTION The subject of the present invention is a mesostructured material consisting of at least two elementary spherical particles, each of said particles comprising a mesostructured matrix based on aluminum oxide, said matrix having a pore diameter of between 1.5 and 30 nm and an aluminum oxide content representing more than 46% by weight relative to the mass of said matrix, which has amorphous walls of thickness between 1 and 30 nm, said elementary spherical particles having a greater diameter D at 10 μm and less than or equal to 100 μm (10 D D (μm) <100). For the purposes of the present invention, the term "mesostructured material" means a material having at least one organized porosity at the mesopore scale of each of said spherical particles, that is to say a pore-scale porosity having a pore size. uniform diameter of between 1.5 and 30 nm and preferably between 1.5 and 10 nm distributed homogeneously and evenly in each of said particles (mesostructuring of the material). More specifically, in the context of the present invention, the mesostructuration of the material is inherent to the matrix, included in said material: the matrix based on aluminum oxide, included in each of said spherical particles constituting the material according to the invention , is mesostructured. It has mesopores having a uniform diameter of between 1.5 and 30 nm and preferably between 1.5 and 10 nm, distributed homogeneously and uniformly in each of said particles. It should be noted that porosity of a microporous nature may also result from the imbrication of the surfactant, used during the preparation of the material according to the invention, with the inorganic wall at the level of the organic-inorganic interface developed during the mesostructuring of the inorganic component of said material according to the invention. The material located between the mesopores of the mesostructured matrix is amorphous and forms walls, or walls, whose thickness is between 1 and 30 nm. The thickness of the walls corresponds to the distance separating a first mesopore from a second mesopore, the second mesopore being the pore closest to the first mesopore. The organization of the mesoporosity described above leads to a structuring of the matrix based on aluminum oxide, which may be hexagonal, vermicular, cholesteric, lamellar, bicontinuous or cubic, and preferably vermicular. The material according to the invention also has an interparticle textural macroporosity. According to the invention, said elementary spherical particles constituting the material according to the invention have a diameter D, expressed in micron, strictly greater than 10 μm and less than or equal to 100 μm (10 D D (μm) 100). Preferably, the diameter D of said spherical particles is advantageously between 11 and 70 m. According to a particular embodiment of the material according to the invention, said elementary spherical particles have a diameter D of between 11 and 50 m and very preferably between 15 and 50 m. More specifically, said elementary spherical particles are present in the material according to the invention in the form of aggregates.

The material according to the invention advantageously has a specific surface area of between 100 and 1200 m 2 / g, advantageously between 200 and 1000 m 2 / g and very advantageously between 300 and 800 m 2 / g. According to a first embodiment of the material according to the invention, the matrix based on aluminum oxide, mesostructured, is entirely aluminum.

According to a second embodiment of the material according to the invention, the matrix based on aluminum oxide, mesostructured, further comprises silicon oxide. The matrix, included in each of the spherical particles of the material according to the invention, is in this case an aluminosilicate. The content of silicon oxide in the aluminosilicate matrix is such that the Si / Al molar ratio is strictly less than 1.

According to a third embodiment of the material according to the invention, each of said spherical particles further comprises zeolitic nanocrystals having a pore opening of between 0.2 and 2 nm. The material according to the invention then has on the scale of said spherical particles not only an organized porosity at the mesopore scale having a uniform diameter of between 1.5 and 30 nm and preferably between 1.5 and 10 nm, distributed in a homogeneous and regular manner in each of said particles (mesostructuration as described above) but also a zeolite-type microporosity whose characteristics (structural type of the zeolite, chemical composition of the zeolite framework) are a function of the choice of zeolitic nanocrystals. According to the third embodiment of the material according to the invention, the zeolitic nanocrystals have a pore opening of between 0.2 and 2 nm, preferably between 0.2 and 1 nm and very preferably between 0.2 and 0. , 6 nm. Said nanocrystals generate the microporosity in each of the elementary spherical particles constituting the material according to the invention. According to this third embodiment of the material according to the invention, said matrix may be either entirely aluminum or further comprise silicon oxide. In the remainder of the description, the material according to the third embodiment will be called a mixed mesostructured / zeolite material. According to the third embodiment of the mesostructured material according to the invention, the zeolitic nanocrystals advantageously represent from 0.1 to 30% by weight, preferably from 0.1 to 20% by weight and very preferably from 0.1 to 10% by weight. % weight of the material of the invention. All zeolites and in particular, but not limited to, those listed in "Atlas of zeolite framework types", 6th revised Edition, 2007, Ch.Baerlocher, LB McCusker, DHOlson can be used in the zeolite nanocrystals present in each of the particles elementary spheres constituting the material according to the invention. The zeolitic nanocrystals preferably comprise at least one zeolite chosen from zeolites ZSM-5, ZSM-48, ZSM-22, ZSM-23, ZBM-30, EU-2, EU-11, Silicalite, Beta, zeolite A, Faujasite , Y, USY, VUSY, SDUSY, mordenite, NU-87, NU-88, NU-86, NU-85, IM-5, IM-12, Ferrierite and EU-1. Very preferably, the zeolitic nanocrystals comprise at least one zeolite chosen from zeolites of structural type MFI, BEA, FAU and LTA. Nanocrystals of different zeolites and in particular zeolites of different structural types may be present in each of the spherical particles constituting the material according to the invention. In particular, each of the spherical particles constituting the material according to the invention may advantageously comprise at least first zeolitic nanocrystals whose zeolite is chosen from zeolites ZSM-5, ZSM-48, ZSM-22, ZSM-23, ZBM -30, EU-2, EU-11, Silicalite, Beta, Zeolite A, Faujasite, Y, USY, VUSY, SDUSY, Mordenite, NU-87, NU-88, NU-86, NU-85, IM-5, IM-12, Ferrierite and EU-1, preferably from the structural type zeolites MFI, BEA, FAU, and LTA and at least second zeolitic nanocrystals whose zeolite is different from that of the first zeolitic nanocrystals and is chosen from zeolites ZSM-5, ZSM-48, ZSM-22, ZSM-23, ZBM-30, EU-2, EU-11, Silicalite, Beta, Zeolite A, Faujasite, Y, USY, VUSY, SDUSY, Mordenite, NU-87 , NU-88, NU-86, NU-85, IM-5, IM-12, Ferrierite and EU-1, preferably among the structural type zeolites MFI, BEA, FAU, and LTA. The zeolitic nanocrystals advantageously comprise at least one zeolite either entirely silicic or containing, in addition to silicon, at least one element T selected from aluminum, iron, boron, indium and gallium, preferably aluminum. The zeolitic nanocrystals have a maximum size of 1000 nm and preferably have a size between 30 and 500 nm. The mesostructured material of the present invention, having a fully aluminosilicate mesostructured matrix or of aluminosilicate nature and possibly having nanocrystals of zeolites trapped within this matrix, can be obtained in the form of powder, beads, pellets, granules, or extrusions, shaping operations being performed by conventional techniques known to those skilled in the art. Preferably, the material according to the invention is obtained in powder form, which consists of elementary spherical particles having a diameter D such that 10 <D (μm) 100, which facilitates the possible diffusion of the compounds in the case of use of the material according to the invention in a potential industrial application. The present invention also relates to the preparation of the material according to the invention. It first proposes to provide a process for preparing the mesostructured material according to the invention comprising a fully aluminosilicate or aluminosilicate mesostructured matrix. A process for the preparation of such a material according to the invention, called the "main preparation process according to the invention", comprises a) mixing in solution at least one surfactant, at least one aluminum precursor and optionally at least one less a silicic precursor; b) the aerosol atomization of the solution obtained in step a) using a spray nozzle which leads to the formation of liquid droplets having a diameter less than or equal to 300 μm; c) drying said droplets, d) grinding the solid product obtained in step c); e) mixing in solution at least one surfactant, at least one aluminic precursor, optionally at least one silicic precursor and at least one fraction of the solid product obtained in step d) so as to form a suspension ; f) the aerosol atomization of the suspension obtained in step e) using a spray nozzle leading to the formation of suspension droplets, which are precursors of the spherical elementary particles having a diameter D such that 10 <D (pm 100 constituents of the material according to the invention; g) drying said droplets obtained in step f) and h) removing said surfactant introduced in said steps a) and e) to obtain a material with mesostructured porosity. Said process is hereinafter referred to as the "main process of preparation according to the invention". The volume percentage of non-volatile compounds present in the suspension according to stage e) of the main preparation process according to the invention is at least equal to 7%, preferably at least 7.5% and even more preferably at least 10%. Said volumetric percentage of non-volatile compounds is defined as the ratio of the volume occupied by the non-volatile inorganic fraction in the form of condensed oxide (s) (AI01.5 and optionally SiO2) in each solid elementary spherical particle obtained after addition atomization of the volume occupied by the non-volatile organic fraction found in the same solid particle (surfactant) on the total volume, the whole being multiplied by 100. More specifically, the volume occupied by the non-volatile inorganic fraction V; norg is defined by the ratio m; norg / p; norg with m; norg = final mass of the inorganic fraction in the form of condensed oxide (s) present in the elementary particle, that is to say AI01,5 and optionally SiO 2 from the inorganic precursors present in step a) and step e) of the main preparation process according to the invention, added with the inorganic fraction of the solid product of step c) of The main method of preparation according to the invention and pinorg is on average equal to 2 (approximation valid for an inorganic fraction of the "aluminosilicate network" type). Similarly, the volume occupied by the nonvolatile organic fraction Vorg is defined by the ratio morg / pore with morg = mass of surfactant present in each elementary spherical particle, that is to say the surfactant present in step a) and in step e) of the main preparation process according to the invention, added with the organic fraction of the solid product of step c) of the main preparation process according to the invention and porg = 1 (approximation valid for a large majority non-volatile organic fraction). The total volume is such that VT = Vinorg + Vorg + Vsolvent, Vinorg and Vorg are defined above and Vsolvant corresponds to the total volume of solvent consisting of water and optionally an organic solvent. According to said main process of preparation according to the invention, the fraction of the solid product obtained in step d) and used for the implementation of said step e) represents from 1 to 100% by weight, preferably from 1 to 80% weight and even more preferably from 5 to 50% by weight of the total amount of solid product ground in step d).

According to a first particular embodiment of the main method of preparation according to the invention, only part of the solid product from step c) is milled during step d) of the process according to the invention; the unmilled portion is generally not reused.

According to a second particular embodiment of the main method of preparation according to the invention, step h) of removing the surfactant is carried out before the grinding step according to step d) so that said step d) is carried out on a solid product free of organic surfactants. Steps a), b), c), h), d), e) and f) become consecutive in the particular case of said second mode of preparation according to the invention are followed by a new drying cycle of the droplets and d removing the surfactant introduced in step e) as described in steps g) and h). For the particular case of the material according to the invention consisting of elementary spherical particles having a diameter D of between 11 and 50 μm, preferably between 15 and 50 μm, it is preferred to use a simplified preparation process called "simplified method of preparation according to the invention "comprising the steps of: a) mixing in solution at least one surfactant, at least one aluminic precursor and optionally at least one silicic precursor; b) the aerosol atomization of the solution obtained in step a) using a spray nozzle which leads to the formation of liquid droplets having a diameter less than or equal to 300 μm; c) drying said droplets, and h) removing said surfactant to obtain a mesostructured porosity material.

According to said simplified method of preparation according to the invention, the volume percentage of non-volatile compounds present in the solution according to step a) of the simplified method of preparation according to the invention is at least equal to 7%, preferably at least equal to at 7.5% and even more preferably at least 10%. Said volumetric percentage of non-volatile compounds is defined as the ratio of the volume occupied by the non-volatile inorganic fraction in the form of condensed oxide (s) (AlO 5 and optionally SiO 2) in each solid elementary spherical particle obtained after atomization plus the volume occupied by the non-volatile organic fraction found in the same solid particle (surfactant) on the total volume, the whole being multiplied by 100. More specifically, the volume occupied by the non-volatile inorganic fraction Vinorg is defined by the ratio minorg / pnorg with minorg = final mass of the inorganic fraction in the form of condensed oxide (s) present in the elementary particle, that is to say AI01,5 and possibly SiO2 resulting from inorganic precursors present in step a) of the simplified process of preparation according to the invention and pinorg is on average equal to 2 (approximation valid for an inorganic fraction of u type "aluminosilicate network"). Similarly, the volume occupied by the non-volatile organic fraction Vorg is defined by the ratio morg / porg with morg = mass of surfactant present in each elementary spherical particle, that is to say the surfactant present in step a) the simplified method of preparation according to the invention and porg = 1 (approximation valid for a large majority of nonvolatile organic fraction). The total volume is such that VT = Vinorg + Vorg + Vsoivant, Vinorg and Vorg are defined above and Vsoivant corresponds to the total volume of solvent consisting of water and optionally an organic solvent. The aluminum precursor and optionally the silicic precursor used in steps a) and e) of the main preparation process according to the invention or in step a) of the simplified preparation process according to the invention are precursors of inorganic oxides well known to those skilled in the art. The aluminum precursor is advantageously an inorganic aluminum salt of formula AIX3, X being a halogen or the NO3 group. Preferably, X is chlorine. It is also possible to use Al2 (SO4) 3 aluminum sulphate as the inorganic salt. The aluminum precursor may also be an organometallic precursor of formula AI (OR ") 3 or R" = ethyl, isopropyl, n-butyl, s-butyl or t-butyl or a chelated precursor such as aluminum acetylacetonate (Al (C5H8O2 ) 3). The aluminum precursor may also be an aluminum oxide or hydroxide. The silicic precursor, if present in steps a) and e) of the main preparation process according to the invention or if it is present in step a) of the simplified preparation process according to the invention, is obtained from any source of silica and preferably a sodium silicate precursor of formula SiO 2, NaOH, a chlorinated precursor of formula SiCl 4, an organometallic precursor of formula Si (OR) 4, where R = H, methyl , ethyl or a chloroalkoxide precursor of formula Si (OR) 4_XCIx wherein R = H, methyl, ethyl, x being between 0 and 4. The silicic precursor may also advantageously be an organometallic precursor of formula Si (OR) 4_XR ' Where R = H, methyl, ethyl and R 'is an alkyl chain or a functionalized alkyl chain, for example by a thiol, amino, R diketone or sulfonic acid group, x being between Oet4.

The surfactant used in steps a) and e) of the main preparation process according to the invention or in step a) of the simplified preparation process according to the invention is an ionic or nonionic surfactant or a mixture of both. Preferably, the ionic surfactant is chosen from phosphonium and ammonium ions and very preferably from quaternary ammonium salts such as ethyltrimethylammonium bromide (CTAB). Preferably, the nonionic surfactant may be any copolymer having at least two parts of different polarities conferring properties of amphiphilic macromolecules. These copolymers may comprise at least one block that is part of the non-exhaustive list of the following families of polymers: fluorinated polymers (- [CH2-CH2-CH2-CH2-O-CO-R1- with R1 = C4F9, C8F17, etc. .), biological polymers such as polyamino acids (poly-lysine, alginates, etc.), dendrimers, polymers consisting of poly (alkylene oxide) chains. In general, any amphiphilic copolymer known to those skilled in the art can be used (S. Forster, M. Antionnetti, Adv.Mater, 1998, 10, 195-217, S. Férster, T.Plantenberg, Angew. Chem., Ed., 2002, 41, 688-714, H. Colfen, Macromol Rapid Rapid, 2001, 22, 219-252). In the context of the present invention, a block copolymer consisting of poly (alkylene oxide) chains is preferably used. Said block copolymer is preferably a block copolymer having two, three or four blocks, each block consisting of a poly (alkylene oxide) chain. For a two-block copolymer, one of the blocks consists of a poly (alkylene oxide) chain of hydrophilic nature and the other block consists of a poly (alkylene oxide) chain of a nature hydrophobic. For a copolymer with three blocks, at least one of the blocks consists of a chain of poly (alkylene oxide) hydrophilic nature while at least one of the other blocks consists of a poly ( alkylene oxide) of hydrophobic nature. Preferably, in the case of a three-block copolymer, the hydrophilic poly (alkylene oxide) chains are poly (ethylene oxide) chains denoted (PEO) x and (PEO) Z and the Poly (alkylene oxide) chains of hydrophobic nature are chains of poly (propylene oxide) denoted (PPO) y, poly (butylene oxide) chains, or mixed chains, each chain of which is a mixture of several alkylene oxide monomers. Very preferably, in the case of a three-block copolymer, a compound of formula (PEO) X (PPO) - (PEO) Z where x is between 5 and 300 and y is between 33 and 300 is used. and z is from 5 to 300. Preferably, the values of x and z are the same. A compound is advantageously used in which x = 20, y = 70 and z = 20 (P123) and a compound in which x = 106, y = 70 and z = 106 (F127). Commercial nonionic surfactants known as Pluronic (BASF), Tetronic (BASF), Triton (Sigma), Tergitol (Union Carbide), Brij (Aldrich) are useful as nonionic surfactants in steps a) and e) the main method of preparation according to the invention or in step a) of the simplified method of preparation according to the invention. For a four-block copolymer, two of the blocks consist of a poly (alkylene oxide) chain of hydrophilic nature and the other two blocks consist of a chain of poly (alkylene oxide) hydrophobic nature.

The atomization step according to steps b) and f) of the main preparation process according to the invention or the atomization step according to step b) of the simplified preparation process according to the invention produces spherical droplets having a diameter less than or equal to 300 m by the use of a spray nozzle, said nozzle being able to be "mono-fluid" or "bi-fluid" (with control of the pressure of a gas such as air compressed or nitrogen) according to the terms known to those skilled in the art. For example nozzles from Spraying System Emani can be used (nozzle "mono-fluid" type N22 or "bi-fluid" type SU4 for example). The size distribution of these droplets is lognormal. The atomization of the solution is done in a chamber into which a carrier gas is sent, a dry air / nitrogen mixture for smaller plants and nitrogen alone for larger installations. According to steps c) and g) of the main preparation process according to the invention or in step c) of the simplified preparation process according to the invention, said droplets are dried. This drying is carried out by contacting said droplets with the above gas, which leads to the gradual evaporation of the solution respectively from the solution, for example from the aquo-organic acid solution or from the organic aquo •• solution, obtained during step a) respectively of step e) of the main process of preparation according to the invention or the progressive evaporation of the solution obtained during step a) of the simplified process of preparation according to the invention, and thus to obtain spherical elementary particles. The outlet temperature for drying in the atomizer chamber is in a range of 80 to 450 ° C. The residence time distribution of the droplets or particles in the atomization chamber is of the order of a few seconds. In step d) of the main process according to the invention, the particles are crushed (Netzsch CGS10 air jet mill for example) and brought back to a few pm (generally 3 to 5 pm). Depending on the installation, the particles are collected at the exit of a cyclone or in a bag filter. The drying of the particles according to steps c) and g) of the main preparation process according to the invention and according to step c) of the simplified method of preparation according to the invention is advantageously followed by a complementary heat treatment at a temperature of between 50 and 300 ° C before removal of the surfactant in step h) of the main process according to the invention or the simplified process according to the invention in order to obtain the material according to the invention with mesostructured porosity. Said removal of the surfactant introduced in steps a) and e) of the main preparation process according to the invention or in step a) of the simplified preparation process according to the invention is advantageously carried out by chemical extraction processes or by heat treatment and preferably by calcination under air in a temperature range of 300 to 1000 ° C and more precisely in a range of 450 to 600 ° C for a period of 1 to 24 hours and preferably for a period of 2 to 6 hours.

The present invention also proposes to provide two alternative main processes for the preparation of a mixed mesostructured / zeolite material according to the invention, that is to say a material in which each of the spherical particles which constitutes it comprises a mesostructured matrix, fully aluminic or of aluminosilicate nature, and zeolitic nanocrystals having a pore opening of between 0.2 and 2 nm.

A first embodiment of one of the two main processes for preparing the material having zeolitic nanocrystals trapped in the mesostructured oxide matrix according to the invention hereinafter referred to as "the first main process for preparing the mixed mesostructured / zeolitic material according to the invention "comprises the same steps a), b), c) d), e), f), g) and h) of the main method of preparation according to the invention described above for the preparation of a mesostructured material having a matrix mesostructured entirely aluminic or of aluminosilicate nature. Said first main process for preparing the mesostructured / zeolitic mixed material according to the invention also comprises a prior step ao) consisting in the synthesis, in the presence of a structuring agent, of nanometer-scale zeolitic nanocrystals having a maximum nanometric size of 1000 nm in order to obtain a colloidal solution in which said nanocrystals are dispersed. Said colloidal solution obtained according to ao) is introduced into the mixture according to steps a) and e) of the main method of preparation according to the invention described above in the present description. Said first main process for preparing the mixed mesostructured / zeolitic material according to the invention therefore comprises: ao) the synthesis, in the presence of at least one structuring agent, of zeolitic nanocrystals of maximum nanometric size equal to 1000 nm in order to obtain a colloidal solution in which said nanocrystals are dispersed; a ') mixing in solution at least one surfactant, at least one aluminic precursor and optionally at least one silicic precursor, and at least one colloidal solution obtained according to ao); b ') the aerosol atomization of the solution obtained in step a') using a spray nozzle which leads to the formation of liquid droplets having a diameter less than or equal to 300 μm; c ') drying said droplets; d) grinding the solid product obtained in step c'); e ') mixing in solution at least one surfactant, at least one aluminum precursor and optionally at least one silicic precursor, at least one colloidal solution obtained according to ao) and at least a fraction of solid product obtained in step d) so as to form a suspension; f ') the aerosol atomization of the suspension obtained in step e') using a spray nozzle leading to the formation of suspension droplets, which are precursors of spherical elementary particles having a diameter D such that 10 <D (pm) s 100 constituting the material according to the invention; g ') drying said droplets obtained in step f') and h ') removing said surfactant introduced in steps a') and e ') to obtain a mixed mesostructured / zeolite material.

The volume percentage of non-volatile compounds present in the suspension according to step e ') of the first main process for preparing the mixed mesostructured / zeolitic material according to the invention is at least equal to 7%, preferably at least 7, 5% and even more preferably at least 10%. Said volumetric percentage of non-volatile compounds is defined as the ratio of the volume occupied by the non-volatile inorganic fraction in the form of condensed oxide (s) in each solid elementary spherical particle obtained after atomization plus the volume occupied by the fraction organic non-volatile found in the same solid particle (surfactant) on the total volume, the whole being multiplied by 100. More specifically, the volume occupied by the non-volatile inorganic fraction Vinorg is defined by the ratio minorg / pinorg with minorg = final waste of the inorganic fraction in the form of condensed oxide (s) present in said elementary spherical particle, that is to say AIO1,5 and optionally SiO2 and nanocrystals of zeolites respectively derived from inorganic precursors and from the stable colloidal solution of zeolite nanocrystals present in step a ') and step e') of the first main process for preparing the mixed mesostructured / zeolitic material according to the invention added to the inorganic fraction of the solid product of step c ') of the first main process for preparing the mixed mesostructured / zeolitic material according to the invention and pinorg is on average equal to 2 (approximation valid for an inorganic fraction of the "aluminosilicate lattice" type). Similarly, the volume occupied by the nonvolatile organic fraction Vorg is defined by the ratio morg / porg with morg = mass of surfactant present in each elementary spherical particle, that is to say the surfactant present in step a ' ) and in step e ') of the first main process for preparing the mixed mesostructured / zeolitic material according to the invention, added with the organic fraction of the solid product of step c') of the first main process for preparing the mixed mesostructured material / zeolitic according to the invention and porg = 1 (approximation valid for a large majority of nonvolatile organic fraction). The total volume is such that Vr = Vinorg + Vorg + Vsoivant, Vinorg and Vorg are defined above and Vsoivant corresponds to the total volume of solvent consisting of water and optionally an organic solvent. According to said first main process for preparing the mixed mesostructured / zeolite material according to the invention, the fraction of the solid product obtained in step d ') and used for the implementation of said step e') represents from 1 to 100% weight, preferably from 1 to 80% by weight and even more preferably from 5 to 50% by weight of the total amount of solid product ground in step d ').

According to a first particular embodiment of said first main process for the preparation of the mesostructured / zeolitic mixed material according to the invention, only a part of the solid product resulting from step c ') is milled during step d) of process according to the invention; the unmilled portion is generally not reused.

According to a second particular embodiment of said first main process for preparing the mesostructured / zeolitic mixed material according to the invention, the surfactant removal step h ') is carried out prior to the grinding step according to the step of ) such that said step d ') is performed on a solid product free of organic surfactants. Steps a '), b'), c '), h'), d ', e') and f ') become consecutive in the particular case of said second mode of preparation of the mixed mesostructured / zeolitic material according to the invention are followed by a new drying cycle of the droplets and removal of the surfactant introduced in step e ') as described in steps g') and h '). For the particular case of the material according to the invention consisting of spherical particles with a diameter D of between 11 and 50 μm, preferably between 15 and 50 μm and comprising a mesostructured matrix, entirely of aluminum or of aluminosilicate nature, and zeolitic nanocrystals having a pore opening between 0.2 and 2 nm, it is preferred to implement a simplified preparation process called "first simplified method for preparing the mixed mesostructured / zeolite material according to the invention" comprising the steps: ao) the synthesis, in the presence of at least one structuring agent of zeolite nanocrystals of maximum nanometric size equal to 1000 nm in order to obtain a colloidal solution in which said nanocrystals are dispersed; a ') mixing in solution at least one surfactant, at least one aluminic precursor and optionally at least one silicic precursor, and at least one colloidal solution obtained according to ao); b ') the aerosol atomization of the solution obtained in step a') using a spray nozzle which leads to the formation of liquid droplets having a diameter less than or equal to 300 μm; c ') drying said droplets, and h') removing said surfactant to obtain a mixed mesostructured / zeolitic material.

According to said first simplified process for preparing the mixed mesostructured / zeolitic material according to the invention, the volume percentage of non-volatile compounds present in the solution according to step a ') of the first simplified process for preparing the mesostructured / zeolitic mixed material according to US Pat. invention is at least 7%, preferably at least 7.5% and even more preferably at least 10%. Said volumetric percentage of non-volatile compounds is defined as the ratio of the volume occupied by the non-volatile inorganic fraction in the form of condensed oxide (s) in each solid elementary spherical particle obtained after atomization plus the volume occupied by the fraction nonvolatile organic substance found in the same solid particle (surfactant) on the total volume, the whole being multiplied by 100. More specifically, the volume occupied by the non-volatile inorganic fraction V; norg is defined by the ratio m; norg / p; norg with m; norg = final mass of the inorganic fraction in the form of condensed oxide (s) present in the elementary particle, that is to say AI01,5 and optionally SiO2 and nanocrystals of zeolites from respectively the inorganic precursors and the stable colloidal solution of the zeolite nanocrystals present in step a ') of the first simplified process for preparing the medium material mesostructured / zeolite xte according to the invention and pinorg is on average equal to 2 (approximation valid for an inorganic fraction of the type "aluminosilicate network"). Similarly, the volume occupied by the nonvolatile organic fraction Vorg is defined by the ratio of jaws / porg with morg = mass of surfactant present in each elementary spherical particle, that is to say the surfactant present in step a ' ) the first simplified process for preparing the mixed mesostructured / zeolite material according to the invention and porg = 1 (approximation valid for a large majority of non-volatile organic fraction). The total volume is such that VT = Vinorg + Vorg + Vsolvent, Vinorg and Vorg are defined above and Vsolvant corresponds to the total volume of solvent consisting of water and optionally an organic solvent.

In accordance with step ao) of the first main process respectively of the first simplified process for preparing the mixed mesostructured / zeolitic material according to the invention, the zeolitic nanocrystals are synthesized according to operating protocols known to those skilled in the art. In particular, the synthesis of zeolite Beta nanocrystals has been described by T. Bein et al., Micropor. Mesopor. Mater., 2003, 64, 165. The synthesis of zeolite Y nanocrystals has been described by T. J. Pinnavaia et al., J. Am. Chem. Soc., 2000, 122, 8791. The synthesis of faujasite zeolite nanocrystals has been described in Kloetstra et al., Microporous Mater., 1996, 6, 287. The synthesis of ZSM-5 zeolite nanocrystals has been described in several publications. R. de Ruiter et al., Synthesis of Microporous Materials, Vol, I; Mr. L. Occelli, H. E. Robson (eds.), Fan Nostrand Reinhold, New York, 1992, 167; A.E. Persson, B.J. Schoeman, J. Sterte, J.-E. Otterstedt, Zeolites, 1995, 15, 611-619. Zeolitic nanocrystals are generally synthesized by preparing a reaction mixture containing at least one silicic source, optionally at least one source of at least one element T selected from aluminum, iron, boron, indium and gallium, preferably at least one aluminum source, and at least one structuring agent.

The reaction mixture is either aqueous or aquo-organic, for example a water-alcohol mixture. The reaction mixture is advantageously placed under hydrothermal conditions under autogenous pressure, optionally by adding gas, for example nitrogen, at a temperature of between 50 and 200 ° C., preferably between 60 and 170 ° C. and even more preferential at a temperature not exceeding 120 ° C until the formation of zeolitic nanocrystals. At the end of said hydrothermal treatment, a colloidal solution is obtained in which the nanocrystals are in the dispersed state. The structuring agent may be ionic or neutral depending on the zeolite to be synthesized. It is common to use the structuring agents of the following non-exhaustive list: nitrogenous organic cations, elements of the family of alkalis (Cs, K, Na, etc.), ether, diamines and any other structuring agent well known to those skilled in the art.

In a second embodiment of the process for preparing the mixed mesostructured / zeolitic material according to the invention, hereinafter referred to as "the second main process for preparing the mixed mesostructured / zeolitic material according to the invention", zeolite crystals are initially used, which have the characteristic of being dispersed in the form of nanocrystals of maximum nanometric size equal to 1000 nm in solution, for example in aqueous-organic acid solution. Said zeolite crystals are introduced into the mixture according to steps a) and e) of the main method of preparation according to the invention described above for the preparation of a mesostructured material having a fully aluminosilicate or aluminosilicate mesostructured matrix. Said second main process for preparing the mixed mesostructured / zeolitic material according to the invention comprises a) the solution mixture of at least one surfactant, at least one aluminum precursor, optionally at least one silicic precursor, and zeolite crystals dispersing in the form of nanocrystals of maximum nanometric size equal to 1000 nm in said solution; b ") aerosolizing the solution obtained in step a") using a spray nozzle which leads to the forming liquid droplets having a diameter less than or equal to 300 μm; c ") drying said droplets, d") grinding the solid product obtained in step c "); e ") mixing in solution at least one surfactant, at least one aluminic precursor, optionally at least one silicic precursor, zeolite crystals dispersing in the form of nanocrystals of maximum nanometric size equal to 1000 nm in said solution and at least a fraction of the solid product obtained in step d ") so as to form a suspension; f ") the aerosol atomization of the suspension obtained in step e") using a spray nozzle leading to the formation of suspension droplets, which are precursors of spherical elementary particles having a diameter D such that 10 <D (pm) 100 constituting the material according to the invention; g ") drying said droplets obtained in step f") and h ") removing said surfactant introduced in steps a") and e ") to obtain a mixed mesostructured / zeolite material. The volume of non-volatile compounds present in the suspension according to step e ") of the second main process for preparing the mixed mesostructured / zeolitic material according to the invention is at least equal to 7%, preferably at least 7.5. % and even more preferably at least 10%. Said volumetric percentage of non-volatile compounds is defined as the ratio of the volume occupied by the non-volatile inorganic fraction in the form of condensed oxide (s) in each solid elementary spherical particle obtained after atomization plus the volume occupied by the fraction organic non-volatile found in the same solid particle (surfactant) on the total volume, the whole being multiplied by 100. More specifically, the volume occupied by the non-volatile inorganic fraction Vinorg is defined by the ratio minorg / pinorg with minorg = final mass of the inorganic fraction in the form of condensed oxide (s) present in the elementary particle, that is to say, Al (31.5 and optionally SiO 2 and nanocrystals of zeolites respectively derived from inorganic precursors and zeolite crystals dispersing in the form of nanocrystals of maximum nanometric size equal to 1000 nm present in step a ") and the step e ") of the second main method for preparing the mesostructured / zeolitic mixed material according to the invention added to the inorganic fraction of the solid product of step c") of the second main process for preparing the mixed mesostructured / zeolitic material according to invention and pinorg is on average equal to 2 (approximation valid for an inorganic fraction of the type "aluminosilicate network"). Similarly, the volume occupied by the non-volatile organic fraction Vorg is defined by the ratio rnorg / porg with morg = mass of surfactant present in each elementary spherical particle, that is to say the surfactant present in step a " ) and step e ") of the second main method for preparing the mesostructured / zeolitic mixed material according to the invention added to the organic fraction of the solid product of step c") of the second main process for preparing the mixed mesostructured material The total volume is such that VT = Vinorg + Vorg + Vsolvent, Vinorg and Vorg are defined above and Vsolvent corresponds to the amount of the total volume. total volume of solvent consisting of water and optionally of an organic solvent, according to said second main process for preparing the mixed mesostructured / zeolitic material e according to the invention, the fraction of the solid product obtained in step d ") and used for the implementation of said step e") represents from 1 to 100% by weight, preferably from 1 to 80% by weight and even more preferably from 5 to 50% by weight of the total amount of solid product ground in step d ").

According to a first particular embodiment of said second main process for preparing the mixed mesostructured / zeolitic material according to the invention, only a part of the solid product resulting from step c ") is milled during step d") of process according to the invention; the unmilled portion is generally not reused.

According to a second particular embodiment of said second main process for preparing the mesostructured / zeolitic mixed material according to the invention, the surfactant removal step h ") is carried out before the grinding stage according to the step d". ) so that said step d ") is carried out on a solid product free of organic surfactants.steps a"), b "), c"), h "), d"), e ") and f ') have become consecutive in the particular case of said second mode of preparation of the mixed mesostructured / zeolite material according to the invention are followed by a new cycle of drying the droplets and removing the surfactant introduced in step e ") as described according to the steps g ") and h"). For the particular case of the material according to the invention consisting of spherical particles with a diameter D of between 11 and 50 μm, preferably between 15 and 50 μm and comprising a mesostructured matrix, entirely of aluminum or of aluminosilicate nature, and zeolitic nanocrystals having a pore opening between 0.2 and 2 nm, it is preferred to implement a simplified preparation process called "second simplified process for preparing the mixed mesostructured / zeolite material according to the invention" comprising the steps of: a) mixing in solution of at least one surfactant, at least one aluminic precursor, optionally at least one silicic precursor, and zeolitic crystals dispersing in the form of nanocrystals of maximum raster size equal to 1000 nm in said solution; aerosolization of the solution obtained in step a) using a spray nozzle which leads to ormation of liquid droplets having a diameter less than or equal to 300 μm; c ") drying said droplets, and h") removing said surfactant introduced in step a ") to obtain a mixed mesostructured / zeolite material.

The percentage by volume of non-volatile compounds present in the solution according to step a ") of the second simplified process for preparing the mesostructured / zeolitic mixed material according to the invention is equal to at least 7%, preferably equal to at least 7%. , 5% and even more preferably at least 10%, said volume percentage of non-volatile compounds is defined as the ratio of the volume occupied by the non-volatile inorganic fraction in the form of condensed oxide (s) in each solid elementary spherical particle obtained after atomization plus the volume occupied by the nonvolatile organic fraction found in the same solid particle (surfactant) on the total volume, the whole being multiplied by 100. More specifically, the volume occupied by the Non-volatile inorganic fraction Vinorg is defined by the ratio nminorg / pinorg with minorg = final mass of the inorganic fraction in oxide form (s) condensate (s) present in the elementary particle, that is to say AI01,5 and optionally SiO2 and nanocrystals of zeolites respectively derived from inorganic precursors and zeolite crystals dispersing in the form of nanocrystals of maximum nanometric size equal to 1000 nm present in step a ") of the second simplified process for preparing the mixed mesostructured / zeolite material according to the invention and pinorg is on average equal to 2 (approximation valid for an inorganic fraction of the" aluminosilicate network "type). Similarly, the volume occupied by the nonvolatile organic fraction Vorg is defined by the ratio morg / porg with morg = mass of surfactant present in each elementary spherical particle, that is to say the surfactant present in step a " ) of the second simplified process for preparing the mixed mesostructured / zeolitic material according to the invention and porg = 1 (approximation valid for a large majority of nonvolatile organic fraction) The total volume is such that VT = Vinorg + Vorg + Vso, , Vinorg and Vorg being defined above and Vsolvent corresponds to the total volume of solvent consisting of water and optionally of an organic solvent In step a ") of the second process (main and simplified) for preparing the mixed mesostructured material zeolite according to the invention, zeolite crystals are used. Any crystallized zeolite known in the state of the art which has the property of being dispersed in solution, for example in aquo-organic acid solution, in the form of nanocrystals of maximum nanometric size equal to 1000 nm is suitable for the implementation of step a ") of the second main method for preparing the mixed mesostructured / zeolite material according to the invention or the second simplified process of the mesostructured / zeolitic mixed material according to the invention, said zeolite crystals are synthesized by methods known from the The zeolitic crystals used in step a ") of the second main process for preparing the mesostructured / zeolitic mixed material according to the invention or the second simplified process of the mixed mesostructured / zeolitic material according to the invention may already be under the form of nanocrystals. Zeolite crystals with a size greater than 1000 nm, for example between 1500 nm and 3 μm, which are dispersed in solution, for example in aqueous-organic solution, preferably in acidic aqueous organic solution, in the form of nanocrystals of size, are advantageously also used. maximum nanometer equal to 1000 nm. Obtaining zeolite crystals dispersing in the form of nanocrystals of nanometer size maximum equal to 1000 nm is also possible by performing functionalization of the surface of the nanocrystals. The zeolitic crystals used are either in their raw form of synthesis, that is to say still containing the structuring agent, or in their calcined form, that is to say freed of said structuring agent. When the zeolitic crystals used are in their raw synthesis form, said structuring agent is removed during step h ") of the second preparation process (second main process or second simplified process respectively) of the mixed mesostructured / zeolitic material according to US Pat. According to the two main processes for preparing the mixed mesostructured / zeolitic material according to the invention, respectively, to the two simplified processes for preparing the mixed mesostructured / zeolitic material according to the invention, the aluminum precursor and optionally the silicic precursor, used in the steps a ') and e') of the first main process for preparing the mixed mesostructured / zeolite material according to the invention respectively in step a ') of the first simplified process for preparing the mixed mesostructured / zeolitic material according to the invention or in the steps a ") and e") of the second main process for preparing the mixed mesostructured / zeolite material according to the invention respectively in step a ") of the second simplified process for preparing the mixed mesostructured / zeolitic material according to the invention are those already given above in the description of the main preparation process according to the invention for the preparation of a mesostructured material having a fully aluminosilicone or aluminosilcate mesostructured matrix. The same applies to the surfactant used in steps a ') and e') of the first main process for preparing the mixed mesostructured / zeolitic material according to the invention, respectively in step a ') of the first simplified process for preparing the mixed mesostructured / zeolitic material according to the invention or in steps a ") and e") of the second main method for preparing the mesostructured / zeolitic mixed material according to the invention respectively in step a ") of the second simplified process of preparation of the mesostructured / zeolitic mixed material according to the invention It may be an ionic or nonionic surfactant A surfactant in the form of a block copolymer consisting of poly (alkylene oxide) chains is particularly A precise description of this form of surfactant is given above in the present description for the preparation of a mesostruct material. formed with a fully aluminosilicate or aluminosilicate mesostructured matrix (steps a or e of the main method of preparation according to the invention).

The solution in which all of the reagents are mixed according to steps a) and e) of the main preparation process according to the invention, respectively according to step a) of the simplified method of preparation according to the invention or according to the steps a ') and e') of the first main process for preparing the mixed mesostructured / zeolitic material according to the invention, respectively according to step a ') of the first simplified process for preparing the mixed mesostructured / zeolitic material according to the invention, or according to steps a ") and e") of the second main process for preparing the mixed mesostructured / zeolite material according to the invention, respectively according to step a ") of the second simplified process for preparing the mixed mesostructured / zeolitic material according to The invention may be acidic, neutral or basic, Preferably said solution referred to above is acidic and has a maximum pH equal to 1 to 3, preferably from 0 to 2. The acids used to obtain an acidic solution having a maximum pH of 3 are, but are not limited to, hydrochloric acid, sulfuric acid and nitric acid. Said solution may be aqueous or may be a water-organic solvent mixture, the organic solvent preferably being a polar solvent miscible with water, in particular THF or an alcohol, in the latter case preferably ethanol. Said solution may also be substantially organic, preferably substantially alcoholic, the amount of water being such that the hydrolysis of the inorganic precursors is ensured (stoichiometric amount). Very preferably, said solution in which at least one aluminum precursor, at least one surfactant and optionally at least one silicic precursor is mixed, is an acidic aqueous-organic mixture, very preferably an acidic-alcoholic water mixture. In the preferred case where the matrix of the material according to the invention contains silicon oxide in addition to aluminum oxide, the concentrations of silicic and aluminic precursors in steps a) and e) of the main preparation process according to the invention, respectively in step a) of the simplified method of preparation according to the invention or in steps a ') and e') of the first main method of preparation of the mixed mesostructured / zeolite material of the invention, respectively in step a ') of the first simplified process for preparing the mesostructured / zeolitic mixed material according to the invention or in steps a ") and e") of the second main process for preparing the mixed mesostructured / zeolitic material according to the invention , respectively in step a ") of the second simplified process for preparing the mixed mesostructured / zeolite material according to the invention are defined by the molar ratio Si / AI, this being strictly less than 1. For the preparation of a mixed mesostructured / zeolitic material according to the invention, the quantity of zeolitic nanocrystals dispersed in the colloidal solution introduced during steps a ') and e') of first main process for preparing the mixed mesostructured / zeolite material according to the invention, respectively during step a ') of the first simplified process for preparing the mesostructured / zeolitic mixed material according to the invention or the quantity of zeolitic crystals introduced during steps a ") and e") of the second main method for preparing the mesostructured / zeolitic mixed material according to the invention, respectively during step a ") of the second simplified process for preparing the mixed mesostructured / zeolite material according to the invention is such that the zeolitic nanocrystals advantageously represent from 0.1 to 30% by weight preferably from 0.1 to 20% by weight and very preferably from 0.1 to 10% by weight of the mixed mesostructured / zeolite material of the invention. The initial concentration of surfactant introduced into the mixture according to steps a) and e) of the main preparation process according to the invention, respectively into the mixture according to step a) of the simplified process according to the invention, or according to the steps a ') and e') of the first main process for preparing the mixed mesostructured / zeolite material according to the invention, respectively according to step a ') of the first simplified process for preparing the mesostructured / zeolitic mixed material according to the invention or according to the steps a ") and e") of the second main process for preparing the mixed mesostructured / zeolite material according to the invention, respectively according to step a ") of the second simplified process for preparing the mixed mesostructured / zeolitic material according to the invention is defined by co and co is defined with respect to the critical micelle concentration (cmc) well known to those skilled in the art. Oncentration limits beyond which occurs the phenomenon of auto-arrangemant surfactant molecules in the solution referred to in each of the 6 processes. The concentration co may be less than, equal to or greater than cmc, preferably less than cmc. In a preferred embodiment of each of the six processes according to the invention (main process of preparation according to the invention and simplified process of preparation according to the invention, first main method of preparation of the mixed mesostructured / zeolitic material according to the invention and first simplified process for preparing the mixed mesostructured / zeolitic material according to the invention, the second main process for preparing the mixed mesostructured / zeolitic material according to the invention and the second simplified process for preparing the mixed mesostructured / zeolitic material according to the invention), concentration co is less than the cmc and said solution referred to in each of the steps a), e), a '), e'), a ") and e") of each of the six preparation processes according to the invention is a mixture acidic water - alcohol.

In the case where the solution referred to in each of the steps a), e), a '), e'), a ") and e") of each of the six preparation processes according to the invention is a water-organic solvent mixture , preferably acid, it is preferred during each of said steps a), e), a '), e'), a ") and e") of each of the six preparation methods according to the invention that the concentration of surfactant at the origin of the mesostructuration of the matrix is less than the critical micellar concentration so that the evaporation of said aqueous-organic solution, preferably acidic, during each of the steps b), f), b '), f '), b ") and f") of each of the six preparation processes according to the invention by the aerosol technique induce a phenomenon of micellization or self-assembly leading to the rnesostructuration of the matrix of the material according to the invention. 'invention. In the case of the preparation of a mixed mesostructured / zeolite material, the mesostructuration of the matrix of the material occurs around the zeolitic nanocrystals which remain unchanged in their shape and their size during the steps b '), f') and c '), g') of the first main process for preparing the mixed mesostructured / zeolite material according to the invention respectively during steps b ') and c') of the first simplified process for preparing the mixed mesostructured / zeolitic material according to the invention or again during steps b "), f") and c "), g") of the second main process for preparing the mixed mesostructured / zeolite material according to the invention respectively during steps b ") and g") of second simplified process for preparing the mixed mesostructured / zeolitic material according to the invention. When co <cmc, the mesostructuration of the matrix of the material according to the invention, prepared according to one of the six processes of the invention, is consecutive to a progressive concentration, within each droplet, of the aluminum precursor, the surfactant, and optionally silicic precursor up to a concentration of surfactant c> cmc resulting from evaporation of the aqueous-organic solution, preferably acidic. In general, the increase in the combined concentration of the aluminum precursor and optionally the silicic precursor, and the surfactant causes the precipitation of the aluminum precursor and optionally the silicic precursor, hydrolyzed (s) around the self-organized surfactant and consequently the structuring of the material according to the invention. Inorganic / inorganic phase interactions, organic / organic phases and organic / inorganic phases lead by a cooperative self-assembly mechanism to the condensation of the hydrolysed aluminum precursor and optionally the hydrolysed silicic precursor around the self-organized surfactant. In the case of the preparation of a mixed mesostructured / zeolitic material, the zeolitic nanocrystals are trapped, during said self-assembly phenomenon, in the mesostructured aluminum oxide matrix included in each of the particles. elementary spheres constituting the material of the invention. The use of spray nozzles is particularly advantageous in order to constrain the reagents present in the initial solution to interact with each other, no loss of material apart from the solvents being possible, all the aluminum elements, possibly silicon and possibly the zeolitic nanocrystals, initially present being thus perfectly preserved (s) throughout each of the three processes according to the invention instead of being eliminated during the filtration and washing steps encountered in conventional synthesis methods known to those skilled in the art. Obtaining spherical elementary particles of diameter D such that 10 <D (Fm) 100 by means of the "EISA" method, in particular by the aerosol technique, specific to the invention requires an increased knowledge and control of the operating parameters. synthesis, essentially in steps a), b), e) and f) of the main process according to the invention or steps a) and b) of the simplified process according to the invention or steps a '), b' ), e ') and f) of the first main method for preparing the mixed mesostructured / zeolite material according to the invention or of steps a') and b ') of the first simplified process for preparing the mixed mesostructured / zeolitic material according to the invention or steps a "), b"), e ") and f ') of the second main process for preparing the mesostructured / zeolitic mixed material according to the invention or steps a") and b ") of the second simplified preparation process mixed mesostructured material / z olithique according to the invention to maintain the mesostructuring process by self-assembly of the surfactant together with the hydrolysis / condensation of various inorganic precursors. In fact, the production of droplets with a diameter of less than or equal to 300 μm leads to evaporation kinetics of the solution or of the aquo-organic suspension all the more slow as the droplet is large (because proportional to the square of the diameter of the the drop to evaporate). If the total evaporation time is slower than the condensation time of the inorganic material at the periphery of the droplet, a layer of condensed material is formed at the evaporation interface providing an additional barrier to evaporation. If this additional layer becomes rigid before sufficient solvent, that is to say water possibly containing organic solvent, has evaporated, the ratio of the volume of the polar constituents to the volume of the non-polar constituents in the mixtures according to the steps a) and e) of the main process of the invention or in the mixture according to step a) of the simplified process according to the invention or in the mixtures according to steps a ') and e') of the first main preparation process of the mixed mesostructured / zeolitic material according to the invention or in the mixture according to step a ') of the first simplified process for preparing the mixed mesostructured / zeolitic material according to the invention or in the mixtures according to steps a ") and e" ) of the second main process for preparing the mesostructured / zeolitic mixed material according to the invention or in the mixture according to step a ") of the second simplified process for preparing the m mixed mesostructured / zeolitic mixed material according to the invention noted Vpol / Vapol = (Vinorg + Vsolvant + Vorg polar) / (hydrophobic Vorg), critical parameter which conditions the appearance of a mesostructuration, is variable between the zones' rigid surface film "and" core of the particle "(with Vinorg = minorg / pinorg as defined above in the present description and Vorg polar + Vorg hydrophobic = Vorg as defined also above in the present description and Vsolvant = total volume of solvent, the solvent being formed of water and optionally of an organic solvent, Vorg polar = volume of the polar parts of the organic reagents, Vorg hydrophobe = volume of the apolar parts of the organic reagents). At the heart, the elements present must then accommodate the mesostructuration to a total volume (defined by the volume inscribed in the rigid crust) higher than the optimal value. If the Vpol / Vapol ratio is too far from the optimum value of mesostructuring, the homogeneity of the mesostructure of the particles produced deteriorates and may disappear to form particles consisting of a well mesostructured crust and a non-mesostructured core (amorphous or good result of a spinoclinal decomposition according to the constitutive elements and the solvents used). In order to avoid this unacceptable phenomenon for the production of the material according to the invention, it is appropriate in steps b) and f) of the main process according to the invention respectively in step b) of the simplified method according to the invention, in steps b ') and f') of the first main process for preparing the mixed mesostructured / zeolite material according to the invention respectively in step b ') of the first simplified process for preparing the mixed mesostructured / zeolitic material according to the invention in steps b ") and f") of the second main process for preparing the mixed mesostructured / zeolite material according to the invention respectively in step b ") of the second simplified process for preparing the mixed mesostructured / zeolitic material according to invention, to limit the volume of solvent to evaporate, in other words, to concentrate the aerosolized solutions in order to work preferentially with a Co value close This results in the presence of non-volatile compounds in the suspension according to step e) of the main preparation process according to the invention and in the solution according to step a) of the simplified process. preparation method according to the invention, according to step e ') of the first main method of preparation of the mixed mesostructured / zeolite material according to the invention and in the solution according to step a') of the first simplified process for preparing the mixed material mesostructured / zeolitic according to the invention, according to step e ") of the second main process for preparing the mixed mesostructured / zeolitic material according to the invention and in the solution according to step a") of the second simplified process for preparing the material mixed mesostructured / zeolitic composition according to the invention, in an amount such that the volume percentage of said compounds present in said suspension / solution is at least 7%. The maximum of this volume percentage is specific to each system and is limited mainly by three criteria: (i) the lack of stability over time of the solutions obtained in steps a) and e) of the main process of the invention respectively to the step a) of the simplified process according to the invention, solutions obtained in steps a ') and e') of the first main process for preparing the mixed mesostructured / zeolite material according to the invention respectively in step a ') of the first process simplified method for preparing the mixed mesostructured / zeolite material according to the invention, the solutions obtained in steps a ") and e") of the second main process for preparing the mixed mesostructured / zeolite material according to the invention respectively in step a ") of the second simplified process for preparing the mixed mesostructured / zeolitic material according to the invention, (ii) the spontaneous precipitation of the solution with too high a ntration (either by lack of solubility of one or more constituents, or by condensation reaction of the inorganic constituents present in solutions obtained in steps a) and e) of the main process of the invention respectively in step a) of the process simplified according to the invention, in steps a ') and e') of the first main process for preparing the mixed mesostructured / zeolite material according to the invention respectively in step a ') of the first simplified process for preparing the mixed mesostructured material / zeolite according to the invention, in steps a ") and e") of the second main process for preparing the mesostructured / zeolite mixed material according to the invention respectively in step a ") of the second simplified process for preparing the mesostructured mixed material / zeolite according to the invention), and (iii) the rheological properties of the solutions obtained in steps a) and and the main process of the invention resp. in step a) of the simplified process according to the invention, in steps a ') and e') of the first main process for preparing the mixed mesostructured / zeolite material according to the invention respectively in step a ') of the first simplified process for preparing the mixed mesostructured / zeolitic material according to the invention, in steps a ") and e") of the second main process for preparing the mixed mesostructured / zeolite material according to the invention respectively in step a ") of the second simplified process for preparing the mesostructured / zeolitic mixed material according to the invention which may become unsuitable for the formation of droplets by the spray nozzles (excessively high viscosity, for example). Steps b '), f), c'), g '), d' and h ') according to the first main process for preparing the mixed mesostructured / zeolite material according to the invention, respectively, the steps b'), c ' ) and h ') according to the first simplified process for preparing the mixed mesostructured / zeolite material according to the invention or the steps b "), f"), c "), g"), d ") and h" "according to the second main process for preparing the mixed mesostructured / zeolitic material according to the invention, respectively, the steps b ") c") and h ") according to the second simplified process for preparing the mixed mesostructured / zeolitic material according to the invention are carried out in the same operating conditions as those in which the steps b), f), c), g), d) and h) of the main process of preparation according to the invention respectivernent steps b), c) and h) of the simplified method of preparation according to the invention are realized.The mesostructured material of the inventio n, optionally having nanocrystals of zeolites trapped within the mesostructured matrix, is characterized by several analysis techniques and in particular by X-ray diffraction at low angles (X-ray at low angles), by X-ray diffraction at large angles ( Large-angle XRD), Nitrogen Volumetry (BET), Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM) and Inductively Coupled Plasma Emission Spectrometry (ICP).

The X-ray diffraction technique at low angles (values of the angle between 0.5 and 6 °) makes it possible to characterize the nanoscale periodicity generated by the organized mesoporosity of the mesostructured matrix of the material of the invention. In the following discussion, the X-ray analysis is performed on powder with a diffractometer operating in reflection and equipped with a rear monochromator using copper radiation (wavelength 1.5406 A). The peaks usually observed on the diffractograms corresponding to a given value of the angle 20 are associated with the inter-reticular distances d (hkl) characteristic of the structural symmetry of the material ((hkl) being the Miller indices of the reciprocal lattice) by the relation of Bragg: 2 d (hkl) * sin (0) = n * This indexation then allows the determination of the parameters of mesh (abc) of the direct network, the value of these parameters being function of the hexagonal structure, cubic, cholesteric, lamellar , bicontinue or vermicular obtained. For example, the low-angle X-ray diffractogram of a mesostructured material consisting of elementary spherical particles comprising an aluminosilicate matrix and obtained according to one of the six methods of preparation described above via the use of the particular block copolymer called poly (ethylene oxide) 20-poly (propylene oxide) 70-poly (ethylene oxide) 20 (PE020-PP070-PE020 or Pluronic 123) has a perfectly resolved correlation peak corresponding to the correlation distance between pores d characteristic of a vermicular type structure and defined by the Bragg relation d (hkl) * sin (A) = n * X. The X-ray diffraction technique at large angles (values of the angle 20 between 5 and 100 °) makes it possible to characterize a crystalline solid defined by the repetition of a unitary unit or unit cell at the molecular scale. It follows the same physical principle as that governing the low-angle X-ray diffraction technique. The wide-angle DRX technique is therefore used to analyze mixed mesostructured / zeolite materials because it is particularly suitable for the structural characterization of the zeolitic nanocrystals present in each of the elementary spherical particles constituting the mixed mesostructured / zeolitic material according to the invention. In particular, it provides access to the pore size of zeolitic nanocrystals. For example, the large and low angle X-ray diffractograms of a mixed mesostructured / zeolite material obtained according to the first or the second process for preparing a mesostructured / zeolitic mixed material according to the invention comprising zeolite nanocrystals of the ZSM type. 5 (MFI), the mesostructured matrix being of aluminosilicate nature and obtained via the use of the particular block copolymer called poly (ethylene oxide) 106-poly (propylene oxide), o-poly (ethylene oxide) 106 (PE0106-PPO70-PE0,06 or F127) respectively exhibit the diffractogram associated with the Pnma symmetry group (No. 62) of the ZSM-5 zeolite at large angles and a perfectly resolved correlation peak at small angles associated with the structure. of the vermicular type of the mesostructured matrix which corresponds to a distance d of correlation between pores. The value of the angle obtained on the diffractogram RX makes it possible to go back to the correlation distance d according to the Bragg law: 2 d (hk,) * sin (0) = n * ~. The values of the mesh parameters a, b, c obtained for the characterization of the nanocrystals of zeolites are consistent with the values obtained for a zeolite of the ZSM-5 type (MFI) well known to those skilled in the art ("Collection of simulated XRD powder patterns for zeolites ", 4th revised edition, 2001, MMJ Treacy, JB Higgins). The nitrogen volumetry corresponding to the physical adsorption of nitrogen molecules in the porosity of the material via a progressive increase of the pressure at constant temperature provides information on the textural characteristics (pore diameter, type of porosity, specific surface) particular of the material according to the invention. In particular, it provides access to the specific surface and the mesoporous distribution of the material. By specific surface is meant the specific surface B.E.T. (SBET in m2 / g) determined by nitrogen adsorption in accordance with ASTM D 3663-78 established from the BRUNAUER-EMMETT-TELLER method described in The Journal of American Society, 1938, 60, 309. The representative porous distribution of a mesopore population centered in a range of 1.5 to 50 nm is determined by the Barrett-Joyner-Halenda model (BJH) The nitrogen adsorption-desorption isotherm according to the BJH model thus obtained is described in the periodical "The Journal of American Society", 1951, 73, 373 written by EP Barrett, LG Joyner and PP Halenda In the following description, the mesospore diameter of the given mesostructured matrix corresponds to the diameter nitrogen adsorption medium defined as being a diameter such that all the pores smaller than this diameter constitute 50% of the pore volume (Vp) measured on the adsorption branch of the nitrogen isotherm. of the adsorption isotherm of Nitrogen and the hysteresis loop can provide information on the nature of the mesoporosity and on the possible presence of microporosity essentially related to zeolitic nanocrystals when they are present in the mesostructured oxide matrix. For example, the nitrogen adsorption isotherm relative to a mesostructured aluminosilicate material according to the invention and obtained by the main method of preparation according to the invention using as surfactant the particular block copolymer called poly (ethylene oxide) ) 20-poly (propylene oxide), opoly (ethylene oxide) 20 (PE020-PP070-PE020 or Pluronic 123 or P123) is characterized by a Class IV adsorption isotherm and a hysteresis loop of type H1 the associated porous distribution curve is representative of a population of mesopores of uniform size centered in a range of 4 to 10 nm. For example of a mesostructured / zeolitic mixed material, the nitrogen adsorption isotherm of such a material obtained according to one of the six processes for preparing a mixed mesostructured / zeolitic material according to the invention and comprising zeolite nanocrystals of the ZSM-5 (MFI) type, the mesostructured matrix being of aluminosilicate nature and obtained via the use of the particular block copolymer called poly (ethylene oxide) 106-poly (propylene oxide) 70-poly ( ethylene oxide) 106 (PE0t06-PP070-PE0106 or F127), for low values of PIPO (where PO is the saturating vapor pressure at temperature T) a typical type I isotherm of a microporous material and for the higher values of P / PO are a type IV isotherm and a type H1 hysteresis loop, the associated porous distribution curve being representative of a population of mesopores of uniform size centered in a range of 4 to 10 nm. Concerning the mesostructured matrix, the difference between the value of the pore diameter 4 and the mesh parameter defined by XRD at low angles as described above gives access to the magnitude e where e = a - $ and is characteristic of the thickness of the amorphous walls of the mesostructured matrix constituting each of the spherical particles of the material according to the invention. Said mesh parameter a is connected to the distance d of correlation between pores by a geometric factor characteristic of the geometry of the phase. For example, in the case of a hexagonal mesh e = a û (with a = 2 * ci /, 3, in the case of a vermicular structure e = d - d.

Transmission electron microscopy (TEM) is also widely used to characterize the structure of these materials. This allows the formation of an image of the studied solid, the contrasts observed being characteristic of the structural organization, the texture or the morphology of the particles observed, the resolution of the technique reaching a maximum of 0.2 nm. In the following description, the TEM photos are made from microtome sections of the sample in order to visualize a section of an elementary spherical particle of the material according to the invention. For example, the MET images obtained for a mesostructured aluminosilicate material according to the invention and obtained by one of the six preparation processes according to the invention using the particular block copolymer called Pluronic 123 have spherical elementary particles having a mesostructure. vermicular, the material being defined by the dark areas. The analysis of the image also makes it possible to access the parameters d, (1) and e characteristics of the mesostructured matrix defined above. For example of a mixed mesostructured / zeolitic material, the TEM images obtained for such a material obtained according to one of the six preparation processes according to the invention comprising zeolite nanocrystals of the ZSM-5 (MFI) type, the mesostructured matrix. being of aluminosilicate nature and obtained via the use of the particular block copolymer called P123 present within the same spherical particle a vermicular mesostructure (the material being defined by dark areas) within which are viewed objects more or less opaque spheres representing the zeolitic nanocrystals trapped in the mesostructured matrix. The analysis of the image also makes it possible to access the parameters d, (1) and e, characteristics of the mesostructured matrix defined above. It is also possible to visualize on this same plate the reticular planes of the nanocrystals instead of the opaque objects mentioned above and thus to go back to the structure of the zeolite.

The morphology and size distribution of the elementary particles were established by scanning electron microscopy (SEM) photo analysis. The structure of the mesostructured matrix constituting each of the particles of the material according to the invention may be cubic, vermicular, cholesteric, lamellar, bicontinuous or hexagonal depending on the nature of the surfactant chosen as structuring agent. Preferably, it is a vermicular structure. The present invention relates to the use of the mesostructured material according to the invention as an adsorbent for the control of pollution or as a molecular sieve for separation. The present invention therefore also relates to an adsorbent comprising the mesostructured material according to the invention. It is also advantageously used as an acidic solid to catalyze reactions, for example those involved in the fields of refining and petrochemistry.

When the mesostructured material according to the invention is used as a catalyst, this material may be associated with an inorganic matrix which may be inert or catalytically active and with a metallic phase. The inorganic matrix may be present simply as a binder to hold together the particles of said material in the various known forms of the catalysts (extrudates, pellets, beads, powders) or may be added as a diluent to impose the degree of conversion in a process which otherwise would progress at too fast a rate, leading to clogging of the catalyst as a result of a significant formation of coke. Typical inorganic matrices are, in particular, support materials for catalysts, such as the various forms of silica, alumina, silica-alumina, magnesia, zirconia, titanium oxides, boron oxides, aluminum phosphates, titanium, zirconium, clays such as kaolin, bentonite, montmorillonite, sepiolite, attapulgite, fuller's earth, synthetic porous materials such as SiOrAl2O3, SiO2-ZrO2, SiO2-ThO2, SiO2-BeO, SiO2 -TiO2 or any combination of these compounds. The inorganic matrix may be a mixture of different compounds, in particular an inert phase and an active phase. Said material of the present invention may also be associated with at least one zeolite and play the role of main active phase or additive. The metal phase can be introduced integrally on said material of the invention. It may also be introduced integrally onto the inorganic matrix or onto the inorganic-solid matrix assembly that is mesostructured by ion exchange or impregnation with cations or oxides chosen from the following elements: Cu, Ag, Ga, Mg, Ca, Sr , Zn, Cd, B, Al, Sn, Pb, V, P, Sb, C: r, Mo, W, Mn, Re, Fe, Co, Ni, Pt, Pd, Ru, Rh, Os, Ir and all other element of the periodic table of elements. The catalyst compositions comprising the material of the present invention are generally suitable for carrying out the main hydrocarbon conversion processes and organic compound synthesis reactions.

The catalyst compositions comprising the material of the invention advantageously find their application in isomerization, transalkylation and disproportionation, alkylation and dealkylation, hydration and dehydration, oligomerization and polymerization, cyclization reactions. , aromatization, cracking, reforming, hydrogenation and dehydrogenation, oxidation, halogenation, hydrocracking, hydroconversion, hydrotreatment, hydrodesulfurization and hydrodenitrogenation, catalytic removal nitrogen oxides, said reactions involving fillers comprising saturated and unsaturated aliphatic hydrocarbons, aromatic hydrocarbons, oxygenated organic compounds and organic compounds containing nitrogen and / or sulfur as well as organic compounds containing other functional groups.

The invention is illustrated by means of the following examples.

Example 1 (Invention): Preparation of a mesostructured aluminosilicate material with a high aluminum content of Si / Al = 0.5 molar ratio obtained from the main process according to the invention. 3.4 kg of aluminum trichloride hexahydrate are added to a solution containing 10 kg of ethanol, 5 l of water, 36 ml of HCl and 1.3 kg of CTAB surfactant. The whole is left stirring at room temperature until complete dissolution of the aluminum precursor. 1.4 kg of tetraethylorthosilicate (TEOS) are then added. After stirring for 10 min at room temperature, the assembly is atomized using a "single-fluid" spray nozzle in a chamber into which a carrier gas, a dry air / nitrogen mixture, is sent. The droplets, obtained by atomization, are dried at 100 ° C. according to the protocol described in the above disclosure of the invention in accordance with step c) of the main preparation process of the invention. The particles are collected in a bag filter. Said particles are crushed using an air jet mill and brought back to a few pm (from 3 to 5 pm). A fraction of: 30% by weight of these crushed particles is then reintroduced into a solution of the same formulation as the initial solution and then the suspension is again atomized using a "mono-fluid" spray nozzle as above and the 20 droplets dried at 100 ° C according to the protocol described in the disclosure of the invention above, according to step g) of the main method of preparation of the invention. The powder collected in a bag filter is then calcined under air for 5 hours at T = 550 ° C. in order to remove the CTAB surfactant. The volume percentage of non-volatile compounds present in the suspension before the second atomization is equal to 8.4%. The solid is characterized by low angle DIRX, nitrogen volumetric, TEM, SEM and ICP. The TEM analysis shows that the final material has an organized mesoporosity characterized by a vermicular structure. The nitrogen volumetric analysis gives a surface area of SBET final material = 510 m2 / g and a mesoporous diameter of 41 = 2.5 nm. The small angle XRD analysis leads to the visualization of a correlation peak at the angle θ = 2.2. The Bragg 2 ratio d * sin (1a1) = 1.5406 makes it possible to calculate the correlation distance d between the pores of the mesotructured matrix, ie d = 4.0 nm. The thickness of the walls of the mesostructured matrix defined by e = d - 4 is therefore e = 1.5 nm. The ICP analysis gives a molar ratio Si / Al equal to 0.5. An SEM image of the spherical elementary particles thus obtained indicates that these particles have a size characterized by a diameter ranging from 15 to 100 μm, the size distribution of these particles being centered around 50 μm.

Example 2 (Invention): Preparation of a mesostructured aluminosilicate material with a high aluminum content of molar ratio Si / Al = 0.9 obtained from the main process according to the invention. 2.6 kg of aluminum trichloride hexahydrate are added to a solution containing 11 kg of ethanol, 5 I of water, 36 ml of HCl and 1.4 kg of surfactant P123. The whole is left stirring at room temperature until complete dissolution of the aluminum precursor. 2 kg of tetraethylorthosilicate (TEOS) are then added. After stirring for 18 hours at room temperature, the whole is atomized using a "single-fluid" spray nozzle in a chamber into which a carrier gas, a dry air / nitrogen mixture, is sent. The droplets, obtained by atomization, are dried at 100 ° C. according to the protocol described in the disclosure of the invention above, in accordance with step c) of the main process according to the invention. The particles are collected in a bag filter. Said particles are crushed using an air jet mill and brought back to a few pm (from 3 to 5 pm). A fraction of 30% by weight of these crushed particles is then reintroduced into a solution of the same formulation as the initial solution, then the suspension is again atomized and the droplets are dried at 100 ° C. according to the protocol described in the disclosure of the invention. above, in accordance with step g) of the main method according to the invention. The powder collected in a bag filter is then calcined under air for 5 hours at T = 550 ° C. so as to eliminate the surfactant P123. The volume percentage of non-volatile compounds present in the suspension before the second atomization is equal to 9.8%. The solid is characterized by low angle XRD, nitrogen volumetric, TEM, SEM and ICP. The TEM analysis shows that the final material has an organized mesoporosity characterized by a vermicular structure. Nitrogen volumetric analysis leads to a specific surface area of the SBET final material = 280 m 2 / g and a mesoporous diameter of 5.6 nm. The small angle XRD analysis leads to the visualization of a correlation peak at the angle θ = 0.64. The Bragg 2 ratio d * sin (0.32) = 1.5406 makes it possible to calculate the correlation distance d between the pores of the mesostructured matrix, ie d = 13.1 nm. The thickness of the walls of the mesostructured matrix defined by e = d - is therefore e = 7.5 nm. ICP analysis gives a molar ratio Si / Al equal to 0.9. An SEM image of the spherical elementary particles thus obtained indicates that these particles have a size characterized by a diameter ranging from 15 to 100 μm, the size distribution of these particles being centered around 50 pm. Example 3 (Invention): preparation of a mesostructured aluminosilicate material with a high aluminum content comprising zeolite nanocrystals of ZSM-5 type (MFI) (molar Si / Al = 100, 10% by weight of the final material) trapped in a mesostructured aluminosilicate matrix (molar Si / Al = 0.9) obtained from the first main process for preparing the mixed mesostructured / zeolitic material according to the invention. 140 g of tri-sec-butoxide of aluminum are added to a solution containing 3.5 l of tetrapropylammonium hydroxide (TPAOH), 10 g of sodium hydroxide and 4.3 l of water. After dissolution of the aluminum alkoxide, 6 kg of tetraethylorthosilicate (TEOS) are added. The solution is stirred at room temperature for 5 h and then autoclaved at T = 95 ° C for 12 h. The white solution obtained contains nanocrystals of ZSM-5 of 135 nm. This solution is centrifuged at 20,000 rpm for 30 minutes. The solid is redispersed in water and then centrifuged again at 20,000 rpm for 30 minutes. This washing is done twice. The nanocrystals form an oven-dried gel overnight at 60 ° C. 460 mg of these crystals are redispersed in a solution containing 11 kg of ethanol, 5 l of water, 2 kg of TEOS, 2.6 kg of AlCl 3, 6H 2 O, 36 ml of HCl and 1.4 kg of surfactant P123. by ultrasonic agitation for 24 hours. The assembly is atomized using a "mono-fluid" spraying nozzle in a chamber into which a carrier gas, a dry air / nitrogen mixture, is sent. The droplets, obtained by atomization, are dried at 100 ° C. according to the protocol described in the above disclosure of the invention, according to step c ') of the first main preparation method according to the invention. The particles are collected in a bag filter. Said particles are crushed using an air jet mill and brought back to a few pm (from 3 to 5 pm). A fraction of 30% by weight of these crushed particles is then reintroduced into a solution of the same formulation as the initial solution and the suspension is again atomized using a "mono-fluid" spray nozzle as above and the droplets dried at 100 ° C according to the protocol described in the disclosure of the invention above, according to step g ') of the first main method of preparation according to the invention. The powder collected in a bag filter is then calcined under air for 5 hours at T = 550 ° C. so as to eliminate the surfactant P123.

The volume percentage of non-volatile compounds present in the suspension before the second atomization is equal to 9.8%. The solid is characterized by low angle XRD, nitrogen volumetric, TEM, SEM and ICP. The TEM analysis shows that the final material consists of nanocrystals of zeolite ZSM-5 entrapped in an aluminosilcate matrix with organized mesoporosity characterized by a vermicular structure.

Nitrogen volumetric analysis leads to a surface area of SBET final material = 310 m2 / g and to a mesoporous diameter characteristic of the mesostructured aluminosilcate matrix of 4 = 5.6 nm. The wide-angle XRD analysis leads to obtaining the diffractogram characteristic of zeolite ZSM-5 (size of the micropores of the order of 0.55 nm). The small-angle XRD analysis leads to the visualization of a correlation peak associated with the vermicular symmetry of the mesostructured matrix. The Bragg relation gives 2 d * sin (0.32) = 1.5406, ie d = 13.1 nm. The thickness of the amorphous walls of the aluminosilicate mesostructured matrix defined by e = d-4 is therefore e = 7.5 nm. The ICP analysis gives a Si / Al molar ratio of the matrix equal to 0.9. An SEM image of the spherical elementary particles thus obtained indicates that these particles have a size characterized by a diameter ranging from 15 to 100 μm, the size distribution of these particles being centered around 50 μm.

Claims (18)

REVENDICATIONS1. Mesostructured material consisting of at least two elementary spherical particles, each of said particles comprising a mesostructured matrix based on aluminum oxide, said matrix having a pore diameter of between 1.5 and 30 nm and an oxide content of aluminum representing more than 46% by weight relative to the mass of said matrix, which has amorphous walls with a thickness of between 1 and 30 nm, said elementary spherical particles having a diameter D greater than 10 μm and less than or equal to 100 μm (10 <D (μm) 100). 2. Material according to claim 1, wherein said spherical particles have a diameter D of between 11 and 70 μm. 3. The material of claim 2 wherein said spherical particles have a diameter D of between 11 and 50 μm. 4. Material according to claim 3, wherein said spherical particles have a diameter D of between 15 and 50 μm. 20 5. Material according to one of claims 1 to 4 such that said mesostructured matrix based on aluminum oxide comprises silicon oxide. 6. The material of claim 5 wherein said mesostructured matrix has a molar ratio Si / Al strictly less than 1. 7. Material according to one of claims 1 to 6 such that said mesostructured matrix has a cubic structure, vermicular, cholesteric, lamellar, bicontinuous or hexagonal. 30 8. Material according to one of claims 1 to 7 as it has a specific surface between 100 and 1200 m2 / g. 9. Material according to one of claims 1 to 8, wherein each of said spherical particles comprises zeolitic nanocrystals having a pore opening of between 0.2 and 2 nm. 25 10. Material according to claim 9, wherein said zeolitic nanocrystals comprise at least one zeolite chosen from zeolites of structural type MFI, BEA, FAU and LTA. 11. The material of claim 9 or 10 such that said zeolitic nanocrystals comprise at least one zeolite all silicic. 12. The material of claim 9 or 10 such that said zeolitic nanocrystals comprise at least one zeolite containing silicon and aluminum. 13. A method for preparing a mesostructured material according to one of claims 1 to 8 comprising a) mixing in solution of at least one surfactant, at least one aluminic precursor and optionally at least one silicic precursor; b) the aerosol atomization of the solution obtained in step a) using a spray nozzle which leads to the formation of liquid droplets having a diameter less than or equal to 300 μm; c) drying said droplets, d) grinding the solid product obtained in step c); e) mixing in solution at least one surfactant, at least one aluminic precursor, optionally at least one silicic precursor and at least one fraction of the solid product obtained in step d) so as to form a suspension ; f) the aerosol atomization of the suspension obtained in step e) using a spray nozzle leading to the formation of suspension droplets, which are precursors of the spherical elementary particles having a diameter D such that 10 <D (pm 100 constituents of the material according to the invention; g) drying said droplets obtained in step f) and h) removing said surfactant introduced in said steps a) and e) to obtain a material with mesostructured porosity. 14. Preparation process according to claim 13 such that the volume percentage of non-volatile compounds present in said suspension according to said step e) is at least equal to 7%. 15. Process for the preparation of a mesostructured material according to one of claims 9 to 12, comprising ao) the synthesis, in the presence of at least one structuring agent, of zeolitic nanocrystals of maximum nanometric size equal to 1'000 nm in order to obtain a colloidal solution in which said nanocrystals are dispersed; a ') mixing in solution at least one surfactant, at least one aluminum precursor and optionally at least one silicic precursor, and at least one colloidal solution obtained according to ao); b ') the aerosol atomization of the solution obtained in step a') using a spray nozzle which leads to the formation of liquid droplets having a diameter less than or equal to 300 μm; c ') drying said droplets; d) grinding the solid product obtained in step c'); e ') mixing in solution at least one surfactant, at least one aluminum precursor and optionally at least one silicic precursor, at least one colloidal solution obtained according to ao) and at least a fraction of solid product obtained in step d) so as to form a suspension; f ') the aerosol atomization of the suspension obtained in step e') using a spray nozzle leading to the formation of suspension droplets, which are precursors of spherical elementary particles having a diameter D such that 10 <D (pm) 100 constituting the material according to the invention; g ') drying said droplets obtained in step f') and h ') removing said surfactant introduced in steps a') and e ') to obtain a mixed mesostructured / zeolite material. 16. Process for preparing a mesostructured material according to claim 15, such that the volume percentage of non-volatile compounds present in said suspension according to said step e ') is at least equal to 7%. 17. A method for preparing a mesostructured material according to one of claims 9 to 12 comprising comprises a ") the solution mixture of at least one surfactant, at least one aluminic precursor, optionally at least one precursor silicic, and zeolite crystals dispersing in the form of nanocrystals of maximum nanometric size equal to 1000 nm in said solution; b ") aerosol atomization of the solution obtained in step a") using a spray nozzle which leads to the formation of liquid droplets having a diameter less than or equal to 300 μm; c ") the drying of said droplets, d") the grinding of the solid product obtained in step c "); e ") mixing in solution at least one surfactant, at least one aluminic precursor, optionally at least one silicic precursor, zeolite crystals dispersing in the form of nanocrystals of maximum nanometric size equal to 1000 nm in said solution and at least a fraction of the solid product obtained in step d ") so as to form a suspension; f ") the aerosol atomization of the suspension obtained in step e") using a spray nozzle leading to the formation of suspension droplets, which are precursors of spherical elementary particles having a diameter D such that 10 <D (pm) <100 constituting the material according to the invention; g ") drying said droplets obtained in step f") and h ") removing said surfactant introduced in steps a") and e ") to obtain a mixed mesostructured / zeolite material. 18. Process for the preparation of a mesostructured material according to claim 17, such that the volume percentage of non-volatile compounds present in said suspension according to said step e ") is at least equal to 7%.